CN103933697B - Compound stabilizer for stabilizing heavy metals in fly ash generated by waste incineration and preparation method of compound stabilizer - Google Patents
Compound stabilizer for stabilizing heavy metals in fly ash generated by waste incineration and preparation method of compound stabilizer Download PDFInfo
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- triethanolamine
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Abstract
The invention relates to a compound stabilizer for stabilizing heavy metals in fly ash generated by waste incineration and a preparation method of the compound stabilizer. The compound stabilizer is prepared from triethanolamine/maleic anhydride/ethylenediamine (TME/MA/ADA-3COONa) and ADA-4CSSNa, wherein TME/MA/ADA-3COONa takes triethanolamine as a core and has a sodium dicarboxylic acid side group and a sodium dithioacid end group, the chemical formula of TME/MA/ADA-3COONa is N[CH2CH2OCOCH2CH2(COONa)N(CSSNa)CH2(CH2)nCH2N(CSSNa)2]3, and n is a positive integer from 0 to 4; the chemical formula of ADA-4CSSNa is (NaSSC)2NCH2(CH2)nCH2N(CSSNa)2, and n is a positive integer from 0 to 4. The compound stabilizer has effective stabilizing action to heavy metals in fly ash generated by waste incineration; with the adoption of the compound stabilizer, the stabilizing treatment is simple in method, the dosage is little, the cost is low, secondary pollution does not exist, and the heavy metal leaching concentration of a fly ash stabilizing product is lower than that in a national stipulation on hazardous waste leaching toxicity; in addition, the compound stabilizer is good in acid and alkali resistance and can be used for lowering the risk that fly ash pollutes the environment after existing in natural environment for a long time.
Description
Technical field
The invention belongs to chemical industry and environmental protection technical field, and in particular to heavy metal in a kind of stable incineration of refuse flyash
Compound stabilizer and preparation method thereof.
Background technology
In recent years " garbage-surrounded city " phenomenon spreads global, and burning disposal is because little, at utmost with floor space
The advantages of realize garbage decrement, innoxious, resource, be increasingly becoming the garbage disposal that developed country in the world generally adopts
Technology, is also the major policies of Chinese government's reply " garbage-surrounded city " phenomenon.It is increasingly serious with " garbage-surrounded city " phenomenon, I
The incineration treatment of garbage scale of state also increases year by year, by 369.9 ten thousand tons of 2003, increases to 35,840,000 tons of 2012,
Increase 969%.2015, China's incineration treatment of garbage scale be up to 112,110,000 tons (《" 12 " whole nation urban life
Installation for rubbish processing to be harmless construction plan》, 2012).
But after waste incineration, the flying dust equivalent to garbage weight 2%～5% can be produced.Flying dust is due to containing national standard
《Consumer waste incineration landfill yard Environmental capacity standard (GB16889-2008)》Explicitly provided danger wastes As, Cd, Cr,
The toxic heavy metals such as Hg, Pb, it is impossible to directly fill, it is necessary to after the Con trolling index that the standard specifies is reached after process, be allowed for access
Household refuse landfill sites are filled.
The processing method of flying dust has：Embathe method, heat treating process, solidification/stabilization method, medicament stabilization method.The method of embathing be with water,
Acid, alkali or other solvents leach to heavy metal in flying dust, but heavy metal enters liquid phase from solid phase, make wastewater treatment again into
For new problem, and processing cost is higher.Heat treatment includes：Sintering, vitrifying, melting, due to using high temperature respectively by flying dust
900～1000 DEG C, 1100～1500 DEG C, more than 1200 DEG C are heated to, then are cooled into amorphous, crystalline form or uniform vitreous
Product.Although heat treatment can effectively stabilizing heavy metal, its construction and operating cost it is all very high, energy consumption is also very big；And
Pyroprocess can produce the melting flying dust of more toxicity, the heavy metal containing higher concentration.Curing/stabilizing, needs to add chemistry
Additive such as cement, flyash, sodium metasilicate, lime etc. first stablize resolidification, most commonly cement solidification/stabilisation, cement
Method low cost, but the quality of original flying dust is dramatically increased (almost twice), the ability of its stabilizing heavy metal is also limited, there is length
The possibility of phase release, meets rainwater, and soluble-salt branch therein oozes out, in long-term natural acid rain environment, heavy metal
Can leach, recontamination soil.
Chemical agent stabilization method is that chemical reaction occurs with the noxious material in flying dust using medicament, is converted into low molten
The process of Xie Xing, low stripping property and hypotoxicity material.Chemical stabilization with respect to other stabilization technologies, can realize waste without
While evilization, reach waste and reduce perhaps not increase-volume, so as to improve overall efficiency and Jing that hazardous waste processes disposal system
Ji property.Chemical agent stabilizing method is because operating cost is low by extensive concern, flying ash especially Japanese in developed country
Main process disposal options be " chemical agent stable+landfill ".
Conventional chemical stabilizer has：(1) inorganic medicament for example lime, phosphoric acid salt, molysite class (ferrous salt, ferriferous oxide),
Carbonate, sulfide (sodium thiosulfate, vulcanized sodium), aluminum oxide, NaOH etc.；(2) organic medicament such as thiocarbamide, ethylenediamine tetraacetic
Acetic acid (EDTA), organic disulfide are for carbaminate and thiophosphate, organic phosphonate, chitosan derivatives etc..
Soluble phosphate stabilizing flying ash from burn is used as Chinese patent application 200510011651.1 is disclosed
Method, soluble phosphate includes orthophosphoric acid, disodium-hydrogen, sodium dihydrogen phosphate, tertiary sodium phosphate, adding when it stabilizes flying dust
Dose is larger, usually the 3%～10% of flying dust weight, will be according to the pH of leachate, if pH from any phosphate>
12, then select the one kind in disodium-hydrogen, sodium dihydrogen phosphate, tertiary sodium phosphate.But PO4 3-Stabilized product, in pH5～9
In environment, H is easily converted into2PO4 -、HPO4 2-(Grubb D.G.,Guimaraes M.S.Valencia R.,
2000.Phosphate immobilization using all acidic type fly ash.J.Hazard.Mater.,
76(2):217-236), so that heavy metal is leached again, and in pH<When 5, phosphate actually heavy metal loses stable
Act on, therefore pH value plays a key effect in the stabilization procedures of soluble phosphoric acid.For flying dust, whether GB HEVP
Method, or the TPLC leaching programs in the U.S., the generally pH of its leachate makes phosphate imitate the stabilisation of flying dust more than 10
Fruit has guarantee.But in long-term natural environment, acid rain can gradually neutralize the alkaline matter of flying dust, and now flying dust is at
pH<In 5 external environment condition, the leaching of heavy metal can quickly increase.Therefore phosphate-stabilized stabilizing fly ash product is antiacid
Scarce capacity, increased its long-term security risks.
Inorganic sulphide is based on insoluble metal sulfide (MS) is generated, so that a huge sum of money to the stabilisation of flying dust
Category is stablized, and chemical feeding quantity is usually 3%～10% (Quina M.J., Bordado J.C.M., Quinta- of flying dust weight
Ferreira R.M.,2010.Chemical stabilization of air pollution control residues
from municipal solid waste incineration.Hazard.Mater.179(1-3):382-392.), but sulphur
Compound is similar with soluble phosphate, and the heavy metal in flying dust could be effectively stablized only in the range of certain pH.
The inorganic salts stabilization agents such as same molysite class, carbonate, hydroxide all have that chemical feeding quantity is big, capacity antacid is poor
Problem.
Organic stabilizer kind mainly has：Thiocarbamide, ethylenediamine tetra-acetic acid (EDTA), organic phosphonate, organic disulfide are for ammonia
Base formates, thiophosphate etc..
The effect of heavy metal is substantially better than inorganic matter vulcanized sodium, the addition of thiocarbamide in the stable flying dust of organic stabilizer thiocarbamide
For flying dust weight 0.7% when, the leaching of Pb can be made less than national standard limit, and vulcanized sodium needs 5% dosage (Zhao
Y.C.,Song L.J.,Li G.J.,2002.Chemical stabilization of MSW incinerator fly
ashes.J.Hazard.Mater.95(1-2):47–63.).The stabilization of thiocarbamide also relies on pH, leachate pH<(pH when 8
=1 digestion agent), the leaching of heavy metal quickly increase (Chen Dan, Qian Guangren, Zhang Houhu, Zhu Huajun, 2006. Tea Saponin it is stable and
Modification incineration of refuse flyash experimental study [J]. Northcentral University's journal (natural science edition) .27 (6):519-523.).
The stabilization of ethylenediamine tetra-acetic acid (EDTA) heavy metal is also relied on pH, it is necessary in pH>(Liu Yuan is used when 10
Unit, Wang Liao, Lin Xiang, Cui Zhiqiang, Luo Yu, Hu Gang, 2007. city garbage burning flying ash heavy metal medicament compatibilities stabilize experiment
Research [J]. environmental project journal, 1 (10):94-99.), therefore EDTA capacity antacids are not also good.
Chinese granted patent ZL 200410067071.X discloses the skill using heavy metal in the stable flying dust of organic phosphonate
Art, but organic phosphonate capacity antacid it is poor (Zhang Houhu etc. the research of the stable incineration of refuse flyash heavy metal of Phosphonic Acid HEDP
[J]. Techniques and Equipment for Environmental Pollution Control, 2006,7 (11)：45-48.).
In recent years, occur in that a class with nabam (DTC) and two thiophosphoryl salt (DTP) as chelate group
The new stabilizing fly ash agent of one class of group, such as Chinese patent application 200410090662.9 is disclosed with polyethyleneimine as basic bone
The nabam class stabilizing fly ash agent of frame；Chinese granted patent 200710190138.2 is disclosed using dialkyl group two
The stabilizing fly ash agent that D2EHDTPA salt compound is compounded with flocculant；Chinese patent application 200810032233.4 is disclosed and made
With the stabilizing fly ash agent of dialkyl dithiocarbamate.These organic stabilizers all works with good stabilizing heavy metal
With.
Above-mentioned inorganic and organic stabilizer evaluation is by old GB《Hazardous waste judging standard-Leaching mirror
Not (GB5086.2-1997)》The effect of medicament is evaluated, with new GB《Household refuse landfill sites Environmental capacity standard
(GB16889-2008)》Enforcement, to stabilizing fly ashization process propose it is tightened up harshness requirement, the leaching concentration of such as Pb
0.25mg/L is reduced to by original 3mg/L, the leaching concentration of Cd is reduced to 0.15mg/L by original 0.3mg/L.Above-mentioned nothing
Machine and organic stabilizer will meet new standard, generally require to add more amounts, and processing cost will be greatly improved.For example use phosphorus
(Zhou Bin etc., 2009), when dosage is 10%, its Pb leaching concentration is when sour sodium processes the flying dust of certain garbage burning factory
0.46mg/L, meets the concentration limit of old GB (GB5086.2-1997) 3mg/L, but can not meet new GB
(GB16889-2008), when chemical feeding quantity for flying dust 30%, the leaching concentration of Pb is 0.27mg/L, still can not meet new state
The concentration limit of mark 0.25mg/L.The enforcement of new national standard is put forward higher requirement to chemical stabilizer.
Therefore, need that to seek a kind of new, efficient, capacity antacid strong badly in terms of the research of incineration of refuse flyash stabilizer
Stabilizer, it is necessary to jump out the circle of above-mentioned existing stabilizer both at home and abroad, the breakthrough sought in structure, and then improve it and fly
The binding ability of heavy metal in ash, the flying dust chemical stabilizer strong to obtaining efficient, capacity antacid.
Polymer is developed so far, and in traditional one-dimensional linear, two dimension crosslinking or Slight branching polymer base, occurs in that
One class has the highly-branched polymers of three-D space structure.Highly branched polymer can be divided into dendroid from architectural feature
Polymer, dissaving polymer, star dissaving polymer, the miscellaneous arm dissaving polymer of star etc..Dendritic has
The polymer of regular texture, dissaving polymer has the polymer of irregular structure.Star polymer refers to three or three
Side chain above is bonded in the dissaving polymer on same centronucleus by chemistry.The complete phase of chemical composition of each side chain
Together, molecular weight should be without difference.Star polymer has three-dimensional flakes structure, is the special highly-branched polymers of a class.
And at least one side chain or molecular size range different from other side chains in chemical composition of Miktoarm star polymer has substantially poor
Not.
Due to the special construction of non-linear polymer, draw with theoretical research value and industrial potential application aspect
The broad interest of people is played.Into 21 century, dendritic has won increasing scientist in world wide
Common concern, has important application prospect in the various fields such as industry, agricultural, national defence, biomedicine, slow-release material, catalysis.
It is of the invention then be triethanolamine be core the star with carboxylic acid sodium side base and carbodithioic acid sodium end group it is hyperbranched
The compound stabilizer of polymer and the carbodithioic acid sodium of Alkylenediamine four composition, has between two kinds of compositions of the compound stabilizer
There is good synergy, not only with the performance of heavy metal in good stable flying dust, and the heavy metal after stablizing has
Excellent resistance soda acid impact capacity, it is ensured that stabilized flying dust long-time stability in the environment.
The content of the invention
It is an object of the invention to overcome, existing inorganic stabilizers and most of organic stabilizer consumption are big, acid-resisting
Not enough weakness, there is provided a kind of to heavy metal stabilizing energy is good in flying dust, it is strong to resist soda acid ability, poly- with new structure
Compound, with the long-term safety requirement for reaching control incineration of refuse flyash stabilization processes cost, meeting flying dust process.
For achieving the above object, the medicament of the stable incineration of refuse flyash that the present invention is provided is a kind of compound stabilizer, should
Compound stabilizer is by the hyperbranched polymerization of star with carboxylic acid sodium side base and carbodithioic acid sodium end group that triethanolamine is core
Thing and the carbodithioic acid sodium of Alkylenediamine four are constituted, and its mol ratio is 1:1.5～3.0.
The triethanolamine core has the knot of the star dissaving polymer of carboxylic acid sodium side base and carbodithioic acid sodium end group
Structure formula is：
N is the positive integer between 0～4 in formula.
The structural formula of the carbodithioic acid sodium of the Alkylenediamine four is：
N is the positive integer between 0～4 in formula.
The preparation method of compound stabilizer proposed by the present invention, concretely comprises the following steps：
(1) maleic anhydride (Maleic anhydride, hereinafter referred to as MA) is added with stirring, reflux condensing tube and temperature
In the four-neck flask of degree meter, dimethyl formamide solution (N, N-Dimethylformamide, hereinafter referred to as DMF) is subsequently adding,
Stir to maleic anhydride dissolving.Under nitrogen and room temperature condition, and dropwise addition triethanolamine (Triethanolamine, hereinafter referred to as
TEA DMF solution), control rate of addition makes temperature be less than 25 DEG C.Stir 30 minutes after completion of dropping, be warming up to 80～90 DEG C,
Reaction 5～10 hours, obtains the star dissaving polymer (Triethanolamine/ of triethanolamine core Malaysia acid end group
3Maleic anhydride, hereinafter referred to as TEA/MA-3COOH).Then 5～10 DEG C are cooled to, alkaline solution is slowly added dropwise, i.e.,
There is white solid to generate, suction filtration, vacuum drying obtains the star of triethanolamine core sodium maleate end group with alcohol flushing twice
Dissaving polymer (hereinafter referred to as TEA/MA-3COONa).Reaction equation is as follows：
(2) by Alkylenediamine (Alkylenediamine, hereinafter referred to as ADA) add with stirring, reflux condensing tube and
In the round-bottomed flask of thermometer, alkaline solution is slowly added dropwise, controls rate of addition, make temperature be less than 10 DEG C.Then slowly drip again
Plus the aqueous solution of the star dissaving polymer (TEA/MA-3COONa) of above-mentioned triethanolamine core sodium maleate end group, control drop
Acceleration, makes temperature be less than 10 DEG C.After completion of dropping, under conditions of nitrogen and 80～90 DEG C, 20～24h is reacted, obtain three
Monoethanolamine core has the star dissaving polymer (Triethanolamine/ of carboxylic acid sodium side base and Alkylenediamine end group
Maleic anhydride/Ethylenediamine, hereinafter referred to as TME/MA/ADA-3COONa) and Alkylenediamine (ADA)
Mixture.Reaction equation is as follows：
N is the positive integer between 0～4 in formula.
(3) to above-mentioned preparation triethanolamine core Alkylenediamine end group star dissaving polymer (TME/MA/ADA-
3COONa) and in the mixture of Alkylenediamine (ADA), alkaline solution is slowly added dropwise, controls rate of addition, make reactant mixture
Temperature is 5～10 DEG C.Then the alcoholic solution of carbon disulfide is added dropwise, rate of addition is controlled, reaction mixture temperature is 5～10 DEG C.
After completion of dropping, in 5～10 DEG C of conditioned response 2～5 hours.Then, 25 DEG C are risen to, continues to react 3～5 hours.Will reaction
Mixed liquor is overnight placed, that is, have white precipitate to separate out, and after filtration, is cleaned with a small amount of alcohol, is refiltered, and obtains target product --- and three
Monoethanolamine is star dissaving polymer (the hereinafter referred to as TEA/ with carboxylic acid sodium side base and carbodithioic acid sodium end group of core
MA/ADA-3COONa-9CSSNa) and the carbodithioic acid sodium (ADA-4CSSNa) of Alkylenediamine four compound stabilizer.Reaction
Equation is as follows：
N is the positive integer between 0～4 in formula.
In the present invention, triethanolamine, maleic anhydride, the mol ratio of alkaline solution are 1 in step (1):3.0～3.1:3.0
～3.1.
In the present invention, the star dissaving polymer (TEA/MA- of triethanolamine core maleate end group in step (2)
3COONa), Alkylenediamine, the mol ratio of alkaline solution are 1:4.0～6.0:4.0～6.0.
In the present invention, the star dissaving polymer (TME/MA/ of triethanolamine core Alkylenediamine end group in step (3)
) and Alkylenediamine mixture (in terms of-NH), carbon disulfide, the mol ratio (NH of alkaline solution ADA-3COONa:CS2:
NaOH it is) 1:1.25～1.50:1.25～1.50.
In the present invention, raw material triethanolamine used, maleic anhydride, carbon disulfide are commercially available product.
In the present invention, Alkylenediamine class used is commercially available product, and its chemical formula is：NH2CH2(CH2)n CH2NH2, its
Middle n is the positive integer between 0～4.
In the present invention, alkaline solution used can be replaced for NaOH with any one in ammoniacal liquor or potassium hydroxide,
The using effect of compound stabilizer, NaOH, potassium hydroxide, ammoniacal liquor is not affected to be commercially available product.
In the present invention, alcohol used is any one in methyl alcohol, ethanol, propyl alcohol or butanol etc., is commercially available product.
Obtained compound stabilizer of the invention is by star dissaving polymer and the carbodithioic acid sodium of Alkylenediamine four
Composition, wherein star dissaving polymer be side base for carboxylic acid sodium, end group be carbodithioic acid sodium, core for triethanolamine star
Shape dissaving polymer, is a kind of new dissaving polymer.Experiment shows, compound stabilizer provided by the present invention, its
Middle triethanolamine is the star dissaving polymer with carboxylic acid sodium side base and carbodithioic acid sodium end group of core, special because of its
Highly branched structure, can effectively stablize the heavy metal in flying dust, and compound with the carbodithioic acid sodium of Alkylenediamine four, have
Collaboration is just promoting effect, and compared with widely used similar medicament on market, chemical feeding quantity is low, possesses good while stabilizing heavy metal
The ability of good antiacid alkali impact.
The compound stabilizer that the present invention is provided can not only effectively stablize the heavy metal in incineration of refuse flyash, with very strong
Resist soda acid impact ability, can be widely applied to incineration of refuse flyash process, it can also be used to the sewage disposal containing heavy metal
Field.
Description of the drawings
In order that the object, technical solutions and advantages of the present invention are clearer, the following examples will combine accompanying drawing to this
Invention is further described, and Fig. 1～6 are using the salpeter solution and sodium hydroxide solution of different pH value as digestion agent,
According to《Solid waste Leaching leaching method hac buffer method (HJ/T300-2007)》Program to stabilisation before and after
The result for carrying out Leaching test, wherein：
Fig. 1 is impacts of the leachate pH to As Leachings.
Fig. 2 is impacts of the leachate pH to Cd Leachings.
Fig. 3 is impacts of the leachate pH to Cr Leachings.
Fig. 4 is impacts of the leachate pH to Ni Leachings.
Fig. 5 is impacts of the leachate pH to Hg Leachings.
Fig. 6 is impacts of the leachate pH to Pb Leachings.
Specific embodiment
Technical scheme is described in further detail below in conjunction with specific embodiment.Finally it should be noted that with
Lower embodiment only to illustrate technical scheme and unrestricted, although having carried out in detail to the present invention with reference to preferred embodiment
Describe in detail it is bright, it will be understood by those within the art that, can to invent technical scheme modify or equivalent,
Without deviating from the spirit and scope of technical solution of the present invention, it all should cover in scope of the presently claimed invention.
Comparative examples below 1～2 is commercially available stabilizer.
Comparative example 1：Organic stabilizer thiocarbamide (H2NCSNH2)。
Comparative example 2：Inorganic stabilizers vulcanized sodium (Na2S)。
Embodiment 1：The preparation of compound stabilizer
29.40g (0.3mol) maleic anhydride (MA) is added into the four-neck flask with stirring, reflux condensing tube and thermometer
In, 29.40g dimethyl formamide solutions (DMF) are subsequently adding, stir to maleic anhydride dissolving, lead to nitrogen, 29.80g is added dropwise
The DMF solution of (50%, 0.1mol) triethanolamine (TEA), control rate of addition makes temperature be less than 25 DEG C.Stir after completion of dropping
30 minutes, 85 DEG C are warming up to, are reacted 5 hours, obtain the star polymer (TEA/MA- of triethanolamine core Malaysia acid end group
3COOH).Then it is cooled to less than 10 DEG C, is slowly added dropwise 24.00g (50%, 0.3mol) sodium hydroxide solution, that is, has white solid
Body is generated, suction filtration, and, vacuum drying, the star for obtaining 50.81g triethanolamine core sodium maleate end groups surpasses with alcohol flushing twice
Branched polymer (TEA/MA-3COONa, yield 99.82%).
31.32g (0.27mol) hexamethylene diamine (1,6-Hexanediamine, hereinafter referred to as HDA) is added with stirring, returned
In the four-neck flask of stream condenser pipe and thermometer, 21.60g (50%, 0.27mol) sodium hydroxide solution, control drop are slowly added dropwise
Acceleration, makes temperature be less than 10 DEG C.Then the water-soluble of 61.08g (50%, 0.06mol) TEA/MA-3COONa is slowly added dropwise again
Liquid, controls rate of addition, makes temperature be less than 10 DEG C.After completion of dropping, under conditions of nitrogen and 80～90 DEG C, 20h is reacted, obtained
To triethanolamine core have carboxylic acid sodium side base and ethylenediamine end group star dissaving polymer (TEA/MA/HDA-3COONa) and
The mixture of hexamethylene diamine (HDA).
Then it is cooled to<10℃.It is slowly added dropwise the sodium hydroxide solution of 86.40g (50.00%, 1.08mol), control drop
Acceleration, makes reaction mixture temperature be less than 10 DEG C.Then the second of 164.16g (50.00%, 1.08mol) carbon disulfide is added dropwise
Alcoholic solution, controls rate of addition, makes reaction mixture temperature be less than 10 DEG C.It is little in 10 DEG C of conditioned response 5 after completion of dropping
When.Then, 25 DEG C are risen to, continues to react 5 hours.Reaction mixture is overnight placed, that is, has white precipitate to separate out, after filtration,
A small amount of ethanol purge is used, is refiltered, obtain 166.25g white products, as triethanolamine core has carboxylic acid sodium side base and two sulphur
For the star dissaving polymer (TEA/MA/HDA-3COONa-9CSSNa) and the carbodithioic acid of hexamethylene diamine four of carboxylic acid sodium end group
The mixture of sodium (HAD-4CSSNa), the mol ratio of wherein TEA/MA/HDA-3COONa-9CSSNa and HAD-4CSSNa is 1:
1.5, yield 96.17%.
Gained compound stabilizer13C nuclear magnetic resoance spectrum (D2O) as shown in figure 1, its characteristic absorption peak is：δ26.801、
26.898、27.055、27.576、28.365、29.172、39.265、47.056、49.815、51.012、57.211、63.129、
66.351、177.216、181.192、206.192、210.052、212.122ppm.Illustrate that the compound stabilizer is triethanolamine
The star dissaving polymer of core carboxylic acid side base carbodithioic acid sodium end group and the mixture of the carbodithioic acid sodium of hexamethylene diamine four
(TEA/MA/HDA-3COONa-9CSSNa+1.5HAD-4CSSNa), its structure is as follows：
Embodiment 2：The preparation of compound stabilizer
Four necks with stirring, reflux condensing tube and thermometer are added to burn 45.08g (0.46mol) maleic anhydride (MA)
In bottle, 45.08g dimethyl formamide solutions (DMF) are subsequently adding, are stirred to maleic anhydride dissolving, lead to nitrogen, be added dropwise
The DMF solution of 44.70g (50%, 0.15mol) triethanolamine (TEA), control rate of addition makes temperature be less than 25 DEG C.Drip
Stir 30 minutes after finishing, be warming up to 85 DEG C, react 7 hours, obtain the star polymer (TEA/ of triethanolamine core Malaysia acid end group
MA-3COOH).Then 10 DEG C are cooled to, the sodium hydrate aqueous solution of 36.80g (50%, 0.46mol) is slowly added dropwise, that is, have white
Color solid is generated, suction filtration, and, vacuum drying obtains the star of 73.92g triethanolamine core sodium maleate end groups with alcohol flushing twice
Shape dissaving polymer (TEA/MA-3COONa, yield 96.82%), it is standby.
17.60g (0.20mol) butanediamine (Isosorbide-5-Nitrae-Butanediamine, hereinafter referred to as BDA) is added with stirring, returned
In the four-neck flask of stream condenser pipe and thermometer, 16.00g (50%, 0.20mol) sodium hydroxide solution, control drop are slowly added dropwise
Acceleration, makes temperature be less than 10 DEG C.Then the water-soluble of 40.72g (50%, 0.04mol) TEA/MA-3COONa is slowly added dropwise again
Liquid, controls rate of addition, makes temperature be less than 10 DEG C.After completion of dropping, under conditions of nitrogen and 80 DEG C, 24h is reacted, obtain three
Monoethanolamine core has the star dissaving polymer (TEA/MA/BDA-3COONa) and fourth two of carboxylic acid sodium side base and ethylenediamine end group
The mixture of amine (BDA).
Then it is cooled to<10℃.It is slowly added dropwise the sodium hydroxide solution of 81.60g (50.00%, 1.02mol), control drop
Acceleration, makes reaction mixture temperature be less than 10 DEG C.Then the second of 155.04g (50.00%, 1.02mol) carbon disulfide is added dropwise
Alcoholic solution, controls rate of addition, makes reaction mixture temperature be less than 10 DEG C.It is little in 10 DEG C of conditioned response 5 after completion of dropping
When.Then, 25 DEG C are risen to, continues to react 7 hours.Reaction mixture is overnight placed, that is, has white precipitate to separate out, after filtration,
A small amount of ethanol purge is used, is refiltered, obtain 100.72g white products, as triethanolamine core has carboxylic acid sodium side base two thio
The star dissaving polymer (TEA/MA/BDA-3COONa-9CSSNa) and the carbodithioic acid sodium of butanediamine four of carboxylic acid sodium end group
(BAD-4CSSNa) mixture, wherein TEA/MA/BDA-3COONa-9CSSNa are 1 with the mol ratio of BAD-4CSSNa:2.0,
Yield 96.29%.
Gained compound stabilizer13C nuclear magnetic resoance spectrum (D2O) as shown in figure 1, its characteristic absorption peak is：δ24.216、
25.982、26.734、38.276、47.341、49.552、50.399、55.391、63.981、66.283、179.296、
183.212、206.239、211.298、215.521ppm.Illustrate that the compound stabilizer is that triethanolamine core carboxylic acid side base two is thio
The star dissaving polymer of carboxylic acid sodium end group and the mixture (TEA/MA/BDA-3COONa- of the carbodithioic acid sodium of butanediamine four
9CSSNa+2.0BAD-4CSSNa), its structure is as follows：
Embodiment 3：The preparation of compound stabilizer
Four necks with stirring, reflux condensing tube and thermometer are added to burn 35.28g (0.36mol) maleic anhydride (MA)
In bottle, 35.28g dimethyl formamide solutions (DMF) are subsequently adding, are stirred to maleic anhydride dissolving, lead to nitrogen, be added dropwise
The DMF solution of 35.76g (50%, 0.12mol) triethanolamine (TEA), control rate of addition makes temperature be less than 25 DEG C.Drip
Stir 30 minutes after finishing, be warming up to 85 DEG C, react 5 hours, obtain the star polymer (TEA/ of triethanolamine core Malaysia acid end group
MA-3COOH).Then it is cooled to less than 10 DEG C, is slowly added dropwise 28.80g (50%, 0.36mol) sodium hydroxide solution, that is, has white
Color solid is generated, suction filtration, and, vacuum drying obtains the star of 60.13g triethanolamine core sodium maleate end groups with alcohol flushing twice
Shape dissaving polymer (TEA/MA-3COONa, yield 97.29%).
16.20g (0.27mol) ethylenediamine (Ethylenediamine, hereinafter referred to as EDA) is added with stirring, backflow
In the four-neck flask of condenser pipe and thermometer, 21.60g (50%, 0.27mol) sodium hydroxide solution is slowly added dropwise, control is added dropwise
Speed, makes temperature be less than 10 DEG C.Then the aqueous solution of 61.08g (50%, 0.06mol) TEA/MA-3COONa is slowly added dropwise again,
Control rate of addition, makes temperature be less than 10 DEG C.After completion of dropping, under conditions of nitrogen and 80～90 DEG C, 20h is reacted, obtained
Triethanolamine core has the star dissaving polymer (TEA/MA/EDA-3COONa) and second of carboxylic acid sodium side base and ethylenediamine end group
The mixture of diamines (EDA).Then it is cooled to<10℃.The NaOH for being slowly added dropwise 86.40g (50.00%, 1.08mol) is molten
Liquid, controls rate of addition, makes reaction mixture temperature be less than 10 DEG C.Then 164.16g (50.00%, 1.08mol) two sulphur is added dropwise
Change the ethanol solution of carbon, control rate of addition, make reaction mixture temperature be less than 10 DEG C.After completion of dropping, in 10 DEG C of bar
Part reacts 5 hours.Then, 25 DEG C are risen to, continues to react 5 hours.Reaction mixture is overnight placed, that is, has white precipitate to analyse
Go out, after filtration, use a small amount of ethanol purge, refilter, obtain 129.39g white products, as triethanolamine core has carboxylic acid sodium
The star dissaving polymer (TEA/MA/EDA-3COONa-9CSSNa) and ethylenediamine tetraacetic of side base and carbodithioic acid sodium end group
The mixture of carbodithioic acid sodium (EAD-4CSSNa), wherein TEA/MA/EDA-3COONa-9CSSNa and EAD-4CSSNa's rubs
You are than being 1:1.5, yield 95.88%.
Gained compound stabilizer13C nuclear magnetic resoance spectrum (D2O) as shown in figure 1, its characteristic absorption peak is：δ38.276、
47.296、53.238、54.783、56.328、64.294、67.355、178.239、181.336、207.392、213.982、
215.238ppm。
Illustrate the hyperbranched polymerization of star that the compound stabilizer is triethanolamine core carboxylic acid side base carbodithioic acid sodium end group
The mixture (TEA/MA/EDA-3COONa-9CSSNa+1.5EAD-4CSSNa) of thing and the carbodithioic acid sodium of hexamethylene diamine four, its knot
Structure is as follows：
Embodiment 4：The stabilization processes of flying ash
Flying ash derives from certain garbage burning factory, and its Leaching detection adopts professional standard《Solid waste leaches poison
Property leaching method hac buffer method (HJ/T300-2007)》The acetic acid of regulation carries out Leaching test, its pollutant control
Standard processed is《Household refuse landfill sites Environmental capacity standard (GB16889-2008)》, test result is shown in Table 1.It can be seen that in the flying dust
The leaching concentration of Pb and Hg is higher, more than the Extraction Toxicity Identification Standard of Hazardous Waste of national regulations, other heavy metal elements without
It is exceeded.
The original fly-ash heavy metal Leaching/mgL of table 1-1
| Content | As | Cd | Cr | Cu | Hg | Ni | Pb | Zn |
| Leaching | 0.022 | 0.101 | 0.012 | 0.139 | 0.149 | 0 | 9.983 | 0.145 |
| National standard limit | 0.3 | 0.15 | 4.5 | 40 | 0.05 | 0.5 | 0.25 | 100 |
The Leaching Heavy Metals of the stabilizing fly ash product of table 2
Obtained to above-described embodiment 1～3 is core with carboxylic acid sodium side base and carbodithioic acid sodium end by triethanolamine
The compound stabilizer of the star dissaving polymer of base and the carbodithioic acid sodium of Alkylenediamine four composition, and comparative example 1,2
Thiocarbamide and vulcanized sodium be applied to incineration of refuse flyash stabilization processes, method is as follows：A certain amount of stabilization agent is dissolved in
In 40ml deionized waters, after stirring, 100g flying ash is added, stirred 30 minutes, form thick shape compound.Then should
Mixture is dried under the conditions of gravity-flow ventilation, as flying ash stabilizing product.
Stabilize product according to《Solid waste Leaching leaching method hac buffer method (HJ/T300-2007)》
Leaching test is carried out, its pollutant catabolic gene standard is《Household refuse landfill sites Environmental capacity standard (GB16889-
2008)》, experimental result is shown in Table 2.
Can be seen that from the data of table 2：The stablizing effect of the compound stabilizer prepared by the present invention very well, when stablizing chemical drug
When the addition of agent is the 0.5% of flying dust weight, the leaching concentration of Pb and Hg is significantly reduced in the stable flying dust of compound stabilizer；
When dosage for flying dust weight 2.0%, the leaching concentration of Pb and Hg is below household refuse landfill sites in stable flying dust
Concentration limit in Environmental capacity standard.
And when the dosage of thiocarbamide is the 10% of flying dust weight in comparative example 1, Pb and Hg in the flying dust after stabilization processes
Leaching concentration be below in household refuse landfill sites Environmental capacity standard being concentration limit.Vulcanized sodium adds in comparative example 2
When measuring 10% for flying dust, the leaching concentration of Hg is below in the flying dust after stabilization processes《Household refuse landfill sites pollution control
Standard (GB16889-2008) processed》In pollutant levels limit value, but the leaching concentration of Pb higher than household refuse landfill sites pollute
Pollutant levels limit value in control standard.
The effect of heavy metal is significantly better than traditional stabilizing fly ash chemical drug in the stable flying dust of compound stabilizer in the present invention
Agent thiocarbamide and vulcanized sodium.
Embodiment 4：The flying dust capacity antacid test of chemical stabilization
Using the salpeter solution of different pH value as digestion agent, according to《Solid waste Leaching leaching method acetic acid delays
Rush solwution method (HJ/T300-2007)》Program the flying dust of the 5% of original flying dust and flying dust quality chemical stabilization is carried out
Leaching is tested, and as a result sees Fig. 1～6.
Because the Comparison of experiment results of the compound stabilizer of the gained of embodiment 1,2,3 is close to, better than conventional stabilizer sulphur
Change sodium and thiocarbamide, therefore it is the thio with carboxylic acid sodium side base and two of core by triethanolamine that Fig. 1～6 are listed obtained by embodiment 1
The star dissaving polymer (TEA/MA/HDA-3COONa-9CSSNa) of carboxylic acid sodium end group and the carbodithioic acid sodium of hexamethylene diamine four
(HAD-4CSSNa) compound stabilizer of composition, pH is leachate pH, rather than digestion agent pH in figure, so that this is better described
The acid-proof alkaline of the medicament of invention.
From the results, it was seen that the flying dust after the compound stabilizer stabilization processes of the present invention, anti acid alkali performance can be excellent, when
(equivalent to being extracted with the acid solution that pH is -0.255～0) during leachate pH 0.98～6.57, As, Cd, Cr, Hg, Ni, Pb's
Leaching concentration is minimum, is less than《Household refuse landfill sites Environmental capacity standard (GB16889-2008)》The Leaching of Heavy Metals of regulation is dense
Degree.Work as pH>(extracted with NaOH aqueous slkalis) when 12.40, the leaching concentration of Pb is minimum, is less than《Household refuse landfill sites pollution control
Standard (GB16889-2008) processed》The Leaching of Heavy Metals concentration of regulation.And traditional stabilizer thiocarbamide and vulcanized sodium then antiacid alkali
Can be very poor.
Therefore the star with carboxylic acid sodium side base and carbodithioic acid sodium end group by triethanolamine for core of the present invention surpasses
The compound stabilizer of branched polymer and the carbodithioic acid sodium of Alkylenediamine four composition, with excellent anti acid alkali performance energy, carries
High security of the stabilized flying dust under long-term natural environment.
Claims (4)
1. in a kind of stable incineration of refuse flyash heavy metal compound stabilizer, it is characterised in that the compound stabilizer is by three
Monoethanolamine is the star dissaving polymer and Alkylenediamine four with carboxylic acid sodium side base and carbodithioic acid sodium end group of core
Carbodithioic acid sodium is constituted, and triethanolamine is the star dissaving polymer with carboxylic acid side base and carbodithioic acid end group of core
It is 1 with the mol ratio of the carbodithioic acid of Alkylenediamine four:(1.5～3.0)；
The triethanolamine is the change with carboxylic acid sodium side base and the star dissaving polymer of carbodithioic acid sodium end group of core
Formula is：N[CH2CH2OCOCH2CH2(COONa)N(CSSNa)CH2(CH2)nCH2N(CSSNa)2]3, n is between 0～4 in formula
Positive integer；Its structural formula is：
N is the positive integer between 0～4 in formula；
The carbodithioic acid Sodium chemistry formula of the Alkylenediamine four is：(NaSSC)2NCH2(CH2)nCH2N(CSSNa)2, n is in formula
Positive integer between 0～4；Its structural formula is：
N is the positive integer between 0～4 in formula.
2. a kind of as claimed in claim 1 preparation method for stablizing the compound stabilizer of heavy metal in incineration of refuse flyash, its
Be characterised by the compound stabilizer be by triethanolamine, maleic anhydride, Alkylenediamine, carbon disulfide, alkali be raw material prepare,
Concretely comprise the following steps：
(1) maleic anhydride is added in the four-neck flask with stirring, reflux condensing tube and thermometer, is subsequently adding dimethyl methyl
Amide solution, stirs to maleic anhydride dissolving；Under nitrogen and room temperature condition, the dimethylformamide that triethanolamine is added dropwise is molten
Liquid, control rate of addition makes temperature be less than 25 DEG C；Stir 30 minutes after completion of dropping, be warming up to 80～90 DEG C, reaction 5～10 is little
When, obtain the star dissaving polymer of triethanolamine core Malaysia acid end group；Then 5～10 DEG C are cooled to, alkalescence is slowly added dropwise
Solution, that is, have white solid to generate, suction filtration, and, vacuum drying obtains triethanolamine core sodium maleate end group with alcohol flushing twice
Star dissaving polymer, reaction equation is as follows：
(2) Alkylenediamine is added in the round-bottomed flask with stirring, reflux condensing tube and thermometer, is slowly added dropwise alkalescence molten
Liquid, controls rate of addition, makes temperature be less than 10 DEG C；Then the star of above-mentioned triethanolamine core sodium maleate end group is slowly added dropwise again
The aqueous solution of dissaving polymer, controls rate of addition, makes temperature be less than 10 DEG C；After completion of dropping, in nitrogen and 80～90 DEG C
Under conditions of, 20～24h is reacted, obtain triethanolamine core and have the star of carboxylic acid sodium side base and Alkylenediamine end group hyperbranched
The mixture of polymer and Alkylenediamine, reaction equation is as follows：
N is the positive integer between 0～4 in formula；
(3) the triethanolamine core prepared to step (2) has the star hyperbranched poly of carboxylic acid sodium side base and Alkylenediamine end group
In the mixture of compound and Alkylenediamine, alkaline solution NaOH is slowly added to, controls rate of addition, make reactant mixture
Temperature is 5～10 DEG C；Then the alcoholic solution of carbon disulfide is added dropwise, rate of addition is controlled, reaction mixture temperature is 5～10 DEG C；
After completion of dropping, in 5～10 DEG C of conditioned response 2～5 hours；Then, 25 DEG C are risen to, continues to react 3～5 hours；Will reaction
Mixed liquor is overnight placed, that is, have white precipitate to separate out, and after filtration, is cleaned with a small amount of alcohol, is refiltered, and obtains target product --- and three
Monoethanolamine is the star dissaving polymer and Alkylenediamine four with carboxylic acid sodium side base and carbodithioic acid sodium end group of core
The compound stabilizer of carbodithioic acid sodium, reaction equation is as follows：
N is the positive integer between 0～4 in formula；
Wherein：Triethanolamine, maleic anhydride, the mol ratio of alkaline solution are 1 in step (1):3.0～3.1:3.0～3.1；Step
Suddenly the star dissaving polymer of triethanolamine core sodium maleate end group, Alkylenediamine, the mol ratio of alkaline solution are in (2)
1:4.0～6.0:4.0～6.0；The star that triethanolamine core has carboxylic acid sodium side base and Alkylenediamine end group in step (3) surpasses
Branched polymer and with the Alkylenediamine mixture of-NH meter, carbon disulfide, alkaline solution NaOH mol ratio as 1:
1.25～1.50:1.25～1.50.
3. preparation method according to claim 2, it is characterised in that the alcohol is to appoint in methyl alcohol, ethanol, propyl alcohol or butanol
One kind, alkaline solution described in step (2) is any one in NaOH, ammoniacal liquor or potassium hydroxide.
4. a kind of compound stabilizer for stablizing heavy metal in incineration of refuse flyash as claimed in claim 1 is used for stabilization processes
Incineration of refuse flyash, it is characterised in that comprise the following steps that：
Compound stabilizer water is prepared into into solution, in being then added to a certain amount of flying ash, addition is flying dust weight
0.5～5%, persistently stir 15～30 minutes, then under the conditions of gravity-flow ventilation be dried, as flying ash stabilizing produce
Thing.
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| CN104399730B (en) * | 2014-09-30 | 2016-09-28 | 同济大学 | A kind of Compound Heavy Metals stabilizer, preparation method and using method thereof containing carbodithioic acid functionalization star-like super-branched polymer |
| CN104672466B (en) * | 2015-02-12 | 2018-01-19 | 同济大学 | Heavy metal-polluted soil is passivated renovation agent dithiocarbamic acid functionalization Alkylenediamine core dendritic and preparation method |
| CN111072122B (en) * | 2019-12-02 | 2022-07-26 | 山东鑫泰水处理技术股份有限公司 | Composite heavy metal chelating agent containing dithio carboxylate functionalized ethoxylated pentaerythritol core hyperbranched polymer |
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| CN112851282A (en) * | 2021-01-27 | 2021-05-28 | 中钢集团马鞍山矿山研究总院股份有限公司 | Gelling agent for solidifying heavy metal ions in tailings and application method thereof |
| CN112972976A (en) * | 2021-02-05 | 2021-06-18 | 南京理工大学 | Method for co-processing solid-liquid phase product of fly ash coal ash hydrothermal reaction |
| CN113648587B (en) * | 2021-09-14 | 2022-06-28 | 同碧(上海)环保科技有限公司 | Waste incineration fly ash stabilizer and processing technology thereof |
| CN116421923A (en) * | 2023-04-12 | 2023-07-14 | 江阴市月城昇利生物科技有限公司 | Preparation method of incineration fly ash treated glucohept composite liquid |
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